S,S-dialkyl-N-substituted phosphoroamidothioates

ABSTRACT

Compounds of the formula ##EQU1## wherein R 1  and R 2  are independently alkyl of 1 to 8 carbon atoms, or alkenyl of 2 to 8 carbon atoms, R 3  is hydrogen or alkyl of 1 to 4 carbon atoms, and R 4  is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of 1 to 4 carbon atoms or an acyl group of 2 to 4 carbon atoms, with the proviso that R 3  and R 4  may be joined to form an alkylene radical of 2 to 5 carbon atoms. The compounds possess insecticidal and herbicidal activity.

This is a division of application Ser. No. 466,433, filed May 2, 1974,now U.S. Pat. No. 3,886,238.

BACKGROUND OF THE INVENTION FIELD

The present invention is directed to phosphoroamidodithionites, moreparticularly S,S-dialkyl-N-mono- and di-substitutedphosphoroamidothionites and their use as insecticides and/or herbicides.

DESCRIPTION OF THE INVENTION

Compounds of the present invention may be represented by the formula##EQU2## wherein R₁ and R₂ are independently alkyl of 1 to 8 carbonatoms, preferably alkyl of 1 to 4 carbon atoms and more preferably alkylof 3 to 4 carbon atoms, or alkenyl of 2 to 8 carbon atoms, preferablyalkenyl of 2 to 4 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbonatoms, R₄ is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4carbon atoms, aryl of 6 to 15 carbon atoms substituted with 0 to 5halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbonatoms, or an acyl group of 2 to 4 carbon atoms, with the proviso that R₃and R₄ may be joined to form an alkylene radical of 2 to 5 carbon atoms,preferably 4 to 5 carbon atoms.

The aryl groups which R₄ may represent are preferably benzyl or phenyl,either being substituted with 0 to 5 halogen atoms of atomic number 9 to35 or alkyl groups of 1 to 4 carbon atoms. More preferably, R₄ is phenylsubstituted with 0 to 2 halogen atoms of atomic number 9 to 17 or alkylof 1 to 2 carbon atoms, and still more preferably, phenyl substitutedwith 0 to 1 chlorine or fluorine atom.

Representative alkyl groups which R₁ , R₂ , R₃ and R₄ may representinclude methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc.Representative alkenyl groups which R₁, R₂ and R₄ may represent includevinyl, allyl, crotyl, etc. R₁ and R₂ may also be pentyl, hexyl, octyl,etc. Preferably R₁ to R₂ will be the same, or will be alkyl. R₄ ispreferably alkyl or aryl optionally substituted as the case may be.

Representative aryl groups which R₄ may represent include phenyl,naphthyl, benzyl, o-chlorophenyl, o-fluorophenyl, o-bromophenyl,p-fluorophenyl, m-chlorophenyl, o-methylphenyl, p-butylphenyl,o-butylphenyl, o,p-dichlorophenyl, pentachlorophenyl,o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronaphthyl, etc.

Representative radicals which R₃ and R₄ joined together with nitrogenmay represent include piperidyl, pyrrolidyl and morpholine.

Representative acyl groups which R₄ may represent include acetyl,propionyl and butyryl.

Representative compounds of the present invention includeS,S-dimethyl-N-butyl phosphoroamidodithionite, S,S-dimethyl-N-phenylphosphoroamidodithionite, S,S-diethyl-N,N-dimethylphosphoroamidodithionite, S,S-dimethyl-N-acetylphosphoroamidodithionite, S-methyl-S-ethyl-N-isopropylphosphoroamidodithionite, S-methyl-S-ethyl-N-vinylphosphoroamidodithionite, S,S-diethyl-N,N-diethylphosphoroamidodithionite, S,S-diisopropyl-N-methylphosphoroamidodithionite, S,S-n-butyl phosphoroamidodithionite,S-methyl-S-hexyl-N-ethyl-N-propionyl phosphoroamidodithionite,S-propyl-S-allyl-N-methyl-N-phenyl phosphoroamidodithionite,S-methyl-S-vinyl-N-methyl phosphoroamidodithionite,S,S-dipropyl-N-2-chlorophenyl phosphoroamidodithionite,S,S-dibutyl-N-2,4-dichlorophenyl phosphoroamidodithionite,S,S-dibutyl-N-2-ethylphenyl phosphoroamidodithionite,S,S-diethyl-N-ethyl-N-2-naphthyl phosphoroamidodithionite,S,S-dibutyl-N-pentachlorophosphoroamidodithionite,S,S-dibutyl-N-2,4-dichloro-3,5-dimethylphenyl phosphoroamidodithionite,S,S-dibutyl-N-piperidyl phosphoroamidodithionite,S,S-dibutyl-N-pyrrolidyl phosphoroamidodithionite, etc.

The compounds of the present invention are prepared by the reaction ofan appropriate S,S-dialiphatic hydrocarbyl phosphorus halide withammonia with a suitable amine or with an appropriate amide according tothe following reaction: ##EQU3## wherein R₁, R₂, R₃ and R₄ are asindicated above and X is a halogen, preferably chlorine.

Generally, the reaction is accomplished by adding the ammonia or amineslowly to the phosphorus chloride. Preferably an excess, e.g., up totwice the molar amount of ammonia, amide or the amine can be used. Theexcess reactant acts as a base acceptor to react with the evolved HX andthereby neutralize it. The reaction is preferably carried out in thepresence of an inert solvent, such as methylene chloride ether, benzene,hexane, etc. Also a molecular seive is preferably present which servesas a drying agent for the solvent amine. The amount of molecular seiveshould be enough to assure substantially complete removal of any H₂ O.

When ammonia is reacted with the phosphorus chloride it is generallypreferable to dissolve the ammonia in the solvent and then add thephosphorus chloride to the ammonia-solvent mixture. When an amine isused, the solvent is preferably added to the phosphorus chloride and theamine added slowly to the phosphorus chloride-solvent mixture.

The above reaction is preferably carried out at a temperature from -78°to 30°C. Following the reaction, the product can be recovered byconventional means. Thus the reaction mixture may be stripped ofsolvent, the product washed with water and dried over magnesium sulfate.

The phosphorus chloride is known in the art and can be prepared as forexample by the procedure in U.S. Patent 3,210,244. Thus a suitablemercaptan may be reacted with phosphorus trichloride to give theS,S-dialiphatic hydrocarbyl phosphorus chloride. If different alkyl oralkenyl groups are desired, two different mercaptans can be reacted withthe phosphorus trichloride.

The present invention can be more fully understood by reference to thefollowing examples.

EXAMPLE 1 Preparation of S,S-di-n-butyl phosphoroamidodithionite

Ammonia (large excess based on the amount of S,S-dibutyl phosphoruschloride) was dissolved in methylene dichloride, cooled to dry icetemperature. A small number of molecular sieves were added. S,S-dibutylphosphorus chloride, 6.5 g. (0.03 mole), was then added slowly. A solidwhite precipitate resulted. The reaction mixture was slowly warmed up toroom temperature and left standing approximately 48 hours. The whitesolid was removed and the remaining solution stripped to obtain an oilhaving the following analysis:

                  Calculated   Found                                              N %            6.2          5.5                                           

EXAMPLE 2 Preparation of S,S-di-n-butyl-N,N-diethylphosphoroamidodithionite

100 ml. of methylene dichloride plus a small amount of molecular sieveswere mixed with 13.05 g. of S,S-di-n-butyl phosphorus chloride. Diethylamine (7.8 g.) was added slowly. The resulting slurry was allowed tostand for approximately 24 hours. The resulting mixture was filtered andstripped to obtain a colorless oil which on chemical analysis showed:

                  Calculated   Found                                              S %            22.8        21.7                                               P %            11.01       11.8                                           

EXAMPLE 3 Preparation of S,S-di-n-butyl-N-pyrrolidylphosphoroamidodithionite

5.84 g. (0.024 mole) of S,S-di-n-butyl phosphorus chloride was dissolvedin approximately 150 ml. of methylene dichloride. A small number ofmolecular sieves were added. Piperidine, 4.06 g. (0.05 mole) was addedslowly. The reaction mixture was cooled in an ice bath during thereaction. The reaction mixture was permitted to stand overnight afterwhich it was filtered and evaporated down to obtain a yellow oil whichwas then dissolved in methylene dichloride, washed twice with water anddried over magnesium sulfate. After isolation, the chemical anaylsisshowed:

                  Calculated   Found                                              S %            21.8        22.1                                               P %            10.6        10.4                                           

EXAMPLE 4 Preparation of S,S-di-n-butyl-N-acetylphosphoroamidodithionite

Under a nitrogen atmosphere, 50 ml. of diethyl ether was dried overseveral molecular sieves. Then, 9.15 g. (0.0373 mole) of S,S-di-n-butylphosphorus chloride was added to the dry ether. Next, 2.21 g. (0.0373mole) of acetamide was added and the reaction mixture turned cloudy.Triethylamine, 3.78 g. (0.0373 mole) was added dropwise. A whiteprecipitate formed, and the reaction mixture was stirred for 1 hour atambient temperature. After warming, the reaction mixture was stirred for24 hours.

The white precipitate was removed by filtration. The resulting solutionslowly formed two layers. After 30 days the layers were separated. Theupper layer weighed 5.30 grams. Analysis:

                  Calculated   Found                                              S %            24.0        26.3                                               P %            11.6        13.8                                           

The NMR spectra was consistent with the assigned structure. The infraredspectra had adsorption peaks at 5.85, 6.85, 7.25, 7.85, 8.1, 8.3 and13.4 microns.

Other compounds of the present invention were prepared substantially asdescribed above and are reported in Table I. All of the compounds areoils.

                                      TABLE I                                     __________________________________________________________________________                                    Elemental Analysis - %                        Ex.                  S           P          Halogen                           No.                                                                                 Compound       Calculated                                                                          Found Calculated                                                                          Found                                                                              Calculated                                                                          Found                       __________________________________________________________________________    5  S,S-n-butyl-N,N-di-n-propyl                                                                     20.7  20.7  10.0  10.0 --    --                             phosphoroamidodithionite                                                   6  S,S-di-n-butyl-N,N-dimethyl                                                                     25.3  25.1  12.2  11.8 --    --                             phosphoroamidodithionite                                                   7  S,S-di-n-butyl-N-methyl                                                                         5.8*  5.3*  --    --   --    --                             phosphoroamidodithionite                                                   8  S,S-di-n-butyl-N,N-di-n-butyl                                                                   19.0  19.0  9.2   8.8  --    --                             phosphoroamidodithionite                                                   9  S,S-diisopropyl-N,N-diethyl                                                                     --    --    12.2  11.8 --    --                             phosphoroamidodithionite                                                   10 S,S-diisopropyl-N,N-di-N-propyl                                                                 22.8  22.3  11.0  10.6 --    --                             phosphoroamidodithionite                                                   11 S,S-di-n-butyl-N-4-chlorophenyl                                                                 10.6**                                                                              10.5**                                                                              --    --   --    --                             phosphoroamidodithionite                                                   12 S,S-di-n-butyl-N-2-fluorophenyl                                                                 6.0** 6.2** --    --   --    --                             phosphoroamidodithionite                                                   13 S,S-diisopropyl-N-4-chlorophenyl                                                                11.5**                                                                              9.8*  10.1  9.2  --    --                             phosphoroamidodithionite                                                   14 S,S-diisopropyl-N-2-fluorophenyl                                                                22.0  21.8  11.6  11.0 --    --                             phosphoroamidodithionite                                                   15 S,S-diisopropyl-N,N-di-n-butyl                                                                  20.7  18.6  10.0  9.2  --    --                             phosphoroamidodithionite                                                   16 S,S-diisopropyl phosphoroamido-                                                                 7.1*  6.6*  --    --   --    --                             dithionite                                                                 17 S,S-diisopropyl-N-methyl                                                                        6.6*  6.1*  --    --   --    --                             phosphoroamidodithionite                                                   18 S,S-diisopropyl-N-ethyl                                                                         28.5  27.0  13.7  12.8 --    --                             phosphoroamidodithionite                                                   19 S,S-diisopropyl-N-n-butyl                                                                       25.3  23.8  12.2  11.6 --    --                             phosphoroamidodithionite                                                   20 S,S-diethyl-N,N-diethyl                                                                         28.5  25.6  13.8  13.0 --    --                             phosphoroamidodithionite                                                   21 S,S-diethyl-N,N-di-n-butyl                                                                      28.5  25.4  13.8  12.1 --    --                             phosphoroamidodithionite                                                   22 S,S-diethyl-N,N-dimethyl                                                                        32.5  30.0  15.7  14.9 --    --                             phosphoroamidodithionite                                                   23 S,S-diethyl-N-ethyl                                                                             32.5  29.6  15.7  14.6 --    --                             phosphoroamidodithionite                                                   24 S,S-di-n-butyl-N-benzyl                                                                         20.4  18.4  9.8   9.1  --    --                             phosphoroamidodithionite                                                   25 S,S-di-n-butyl-N-allyl                                                                          24.2  21.9  11.7  10.6 --    --                             phosphoroamidodithionite                                                   26 S,S-di-n-propyl-N,N-diethyl                                                                     25.3  23.6  12.2  11.3 --    --                             phosphoroamidodithionite                                                   27 S,S-di-n-propyl-N-n-butyl                                                                       25.3  25.1  12.2  11.3 --    --                             phosphoroamidodithionite                                                   28 S,S-di-n-propyl-N,N-dimethyl                                                                    28.5  27.5  13.8  12.5 --    --                             phosphoroamidodithionite                                                   29 S,S-di-n-propyl-N-methyl                                                                        30.4  30.3  14.6  14.8 --    --                             phosphoroamidodithionite                                                   30 S,S-di-n-propyl-N-piperidyl                                                                     24.2  21.9  11.7  10.6 --    --                             phosphoroamidodithionite                                                   31 S,S-di-n-propyl-N,N-di-n-propyl                                                                 22.8  21.1  11.0  10.4 --    --                             phosphoroamidodithionite                                                   32 S,S-di-n-propyl-N-benzyl                                                                        22.3  22.5  10.8  10.4 --    --                             phosphoroamidodithionite                                                   33 S,S-di-n-propyl-N-allyl                                                                         27.1  23.9  13.1  13.0 --    --                             phosphoroamidodithionite                                                   34 S,S-di-n-propyl-N-2-fluorophenyl                                                                22.0  20.0  10.6  10.5 --    --                             phosphoroamidodithionite                                                   35 S,S-di-n-propyl-N-ethyl                                                                         28.5  29.0  13.8  13.6 --    --                             phosphoroamidodithionite                                                   36 S,S-di-n-propyl-N-n-butyl                                                                       20.7  20.5  10.0  10.0 --    --                             phosphoroamidodithionite                                                   37 S,S-di-n-octyl-N-methyl                                                                         18.2  17.6  8.8   8.2  --    --                             phosphoroamidodithionite                                                   38 S,S-di-n-octyl-N-piperidyl                                                                      15.8  14.8  7.6   7.2  --    --                             phosphoroamidodithionite                                                   39 S,S-di-n-octyl-N-butyl                                                                          16.3  15.0  7.9   7.7  --    --                             phosphoroamidodithionite                                                   40 S,S-n-propyl-N-acetyl-N-                                                                        20.3  21.3  9.9   10.4 --    --                             phenyl phosphoroamidodithionite                                            41 S,S-di-n-propyl-N-acetyl                                                                        26.8  26.3  13.0  12.1 --    --                             phosphoroamidodithionite                                                   42 S,S-di-i-propyl-N-butyryl                                                                       24.0  23.6  11.6  11.5 --    --                             phosphoroamidodithionite                                                   43 S,S-di-i-propyl-N-acetyl                                                                        --    --    12.9  11.8 0.0** 0.19*                          phosphoroamidodithionite                                                   44 S,S-di-n-butyl-N-propionyl                                                                      --    --    10.5  10.9 4.7*  3.2*                           phosphoroamidodithionite                                                   __________________________________________________________________________     *nitrogen-                                                                    **halogen                                                                

The compounds of the present invention are, in general, herbicidal inboth pre- and post-emergence applications. For preemergence control ofundesirable vegetation these compounds will be applied in herbicidalquantities to the environment, e.g., soil infested with seeds and/orseedlings of such vegetation. Such application will inhibit the growthof or kill the seeds, germinating seeds and seedlings. Forpost-emergence applications the compounds of the present invention willbe applied directly to the foliage and other plant parts. Generally theyare effective against weed grasses as well as broadleaved weeds. Somemay be selective with respect to type of application and/or type ofweed.

Pre- and post-emergence herbicidal tests on representative compounds ofthis invention were made using the following methods:

PRE-EMERGENCE TEST

An acetone solution of the test compound was prepared by mixing 750 mg.compound, 220 mg. of a nonionic surfactant and 25 ml. of acetone. Thissolution was added to approximately 125 ml. of water containing 156 mg.of surfactant.

Seeds of the test vegetation were planted in a pot of soil and thecompound solution was sprayed uniformly onto the soil surface at a doseof 100 micrograms per cm². The pot was watered and placed in agreenhouse. The pot was watered intermittently and was observed forseedling emergence, health of emerging seedlings, etc. for a 3-weekperiod. At the end of this period the herbicidal effectiveness of thecompound was rated based on the physiological observations. A 0 to 100scale was used; 0 representing no phytotoxicity, 100 representingcomplete kill.

POST-EMERGENCE TEST

The test compound was formulated in the same manner as described abovefor the pre-emergence test. The concentration of the compound in thisformulation was 5000 ppm. This formulation was uniformly sprayed on 2replicate pots of 24-day-old plants (approximately 15 to 25 plants perpot) at a dose of 100 micrograms per cm². After the plants had dried,they were placed in a greenhouse and then watered intermittently attheir bases as needed. The plants were observed periodically forphytotoxic effects and physiological and morphological responses to thetreatment. After 3 weeks the herbicidal effectiveness of the compoundwas rated based on these observations. A 0 to 100 scale was used; 0representing no phytotoxicity, 100 representing complete kill.

The results of these tests appear in Table II.

                                      TABLE II                                    __________________________________________________________________________                                 Herbicidal Effectiveness - %                        Compound       O    W    C     M     P     L                               __________________________________________________________________________    S,S-di-n-butyl-N,N-diethyl                                                                      --/93                                                                              93/85                                                                              100/100                                                                             --/100                                                                              100/100                                                                             100/100                         phosphoroamidodithionite                                                      S,S-n-butyl-N,N-di-n-propyl                                                                     --/100                                                                             --/100                                                                             --/100                                                                              --/100                                                                              --/100                                                                              --/100                          phosphoroamidodithionite                                                      S,S-di-n-butyl-N,N-dimethyl                                                                     --/85                                                                              --/85                                                                              --/80 --/95 --/85 --/65                           phosphoroamidodithionite                                                      S,S-di-n-butyl phosphoroamido-                                                                  65/85                                                                              --/90                                                                              90/-- 80/100                                                                              --    --/75                           dithionite                                                                    S,S-di-n-butyl-N-methyl                                                                         --/95                                                                              70/80                                                                              100/75                                                                              95/100                                                                              90/-- 90/80                           phosphoroamidodithionite                                                      S,S-di-n-butyl-N,N-di-n-butyl                                                                   --/90                                                                              --/75                                                                              --    --/75 --    --                              phosphoroamidodithionite                                                      S,S-diisopropyl-N,N-diethyl                                                                     --   --/70                                                                              --    --/90 --    --                              phosphoroamidodithionite                                                      S,S-diisopropyl-N,N-di-n-propyl                                                                 --   --/70                                                                              --    --/60 --/55 --                              phosphoroamidodithionite                                                      S,S-di-n-butyl-N-2-fluorophenyl                                                                 --   --   --    --/80 --/95 --/55                           phosphoroamidodithionite                                                      S,S-diisopropyl-N,N-di-n-butyl                                                                  --   --   --    --/100                                                                              75/-- --/70                           phosphoroamidodithionite                                                      S,S-diisopropyl phosphoroamido-                                                                 --   --   --    80/-- 70/-- --                              dithionite                                                                    S,S-diisopropyl-N-methyl                                                                        --   --   --    70/-- 80/-- --                              phosphoroamidodithionite                                                      S,S-di-n-butyl-N-pyrrolidyl                                                                     95/100                                                                             70/75                                                                              100/--                                                                              95/100                                                                              --/100                                                                              90/90                           phosphoroamidodithionite                                                      S,S-diisopropyl-N-ethyl                                                                         --   100/--                                                                             --    --    --    --                              phosphoroamidodithionite                                                      S,S-diisopropyl-N-n-butyl                                                                       100/--                                                                             100/--                                                                             80/-- --/90 --/60 --/60                           phosphoroamidodithionite                                                      S,S-di-n-octyl-N-methyl                                                                         --   --   --    --/70 --/60 --                              phosphoroamidodithionite                                                      S,S-di-n-octyl-N-piperidyl                                                                      --   --   75/-- --    --    --                              phosphoroamidodithionite                                                      S,S-diethyl-N-N-diethyl                                                                         --/90                                                                              --/90                                                                              --    --/95 --/95 --/100                          phosphoroamidodithionite                                                      S,S-diethyl-N,N-di-n-butyl                                                                      --/80                                                                              --/80                                                                              --/90 --/100                                                                              --/95 --/95                           phosphoroamidodithionite                                                      S,S-diethyl-N,N-dimethyl                                                                        --   --/70                                                                              --/80 --/80 --/70 --/100                          phosphoroamidodithionite                                                      S,S-diethyl-N-ethyl                                                                             --   --   80/75 --/100                                                                              --/85 --/100                          phosphoroamidodithionite                                                      S,S-di-n-butyl-N-benzyl                                                                         --/95                                                                              --/90                                                                              100/90                                                                              95/100                                                                              95/100                                                                              95/100                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-acetyl                                                                        100/--                                                                             100/--                                                                             100/--                                                                              100/--                                                                              100/--                                                                              100/100                         phosphoroamidodithionite                                                      S,S-di-i-propyl-N-butyryl                                                                       --   --   --    85/-- --    --                              phosphoroamidodithionite                                                      S,S-di-i-propyl-N-acetyl                                                                        --   --   --    100/--                                                                              90/-- 85/--                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-diethyl                                                                     --/95                                                                              --/95                                                                              --/95 --/90 --/100                                                                              100/100                         phosphoroamidodithionite                                                      S,S-di-n-propyl-N-n-butyl                                                                       --/100                                                                             --/100                                                                             --/95 --/100                                                                              --/100                                                                              --/100                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-dimethyl                                                                    --   --/75                                                                              --    --/80 --/95 --/100                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-piperidyl                                                                     --/85                                                                              --/80                                                                              100/80                                                                              --/100                                                                              95/100                                                                              95/100                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-methyl                                                                        100/--                                                                             80/85                                                                              100/90                                                                              100/100                                                                             100/100                                                                             100/100                         phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-di-n-propyl                                                                 --/90                                                                              --/95                                                                              100/95                                                                              --/100                                                                              --/100                                                                              90/100                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-benzyl                                                                        --   70/--                                                                              100/--                                                                              100/--                                                                              100/--                                                                              100/75                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-allyl                                                                         100/--                                                                             --   80/-- --    --    95/--                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-ethyl                                                                         95/--                                                                              --   --    --    90/-- --                              phosphoroamidodithionite                                                      S,S-di-n-butyl-N-propionyl                                                                      --   --/75                                                                              --    80/90 80/-- --                              phosphoroamidodithionite                                                      S,S-di-n-butyl-N-acetyl                                                                         --/100                                                                             --/100                                                                             100/100                                                                             100/100                                                                             70/100                                                                              80/100                          phosphoroamidodithionite                                                      __________________________________________________________________________     O = Wild Oats (Avena fatua)                                                   W = Watergrass (Echinochloa crusgalli)                                        C = Crabgrass (Digitaria sanguinalis)                                         M = Mustard (Brassica arvensis)                                               P = Pigweed (Amaranthus retroflexus)                                          L = Lamsquarter (Chenopodium album)                                      

The amount of compound administered will vary with the particular plantpart or plant growth medium which is to be contacted, the generallocation of application, i.e., sheltered areas such as greenhouses ascompared to exposed areas such as fields, as well as the desired type ofcontrol. For pre-emergent control of most plants dosages in the range ofabout 0.5 to 20 lbs. per acre will be used. Such administration willgive a concentration of about 2 to 80 ppm. compound distributedthroughout 0.1 acre-foot. For post-emergence application, such as foliarspray application, compositions containing about 0.5 to 8 lbs. compoundper 100 gal. spray will be used. Such application is equivalent to about0.5 to 20 lbs. compound per acre.

The herbicidal compositions of this invention comprise a herbicidalamount of one or more of the above described compounds intimatelyadmixed with a biologically inert carrier. The carrier may be a liquiddiluent such as water or acetone or a solid. The solid may be in theform of dust powder or granules. These compositions will also usuallycontain adjuvants such as a wetting or dispersing agent to facilitatetheir penetration into the plant growth media or plant tissue andgenerally enhance their effectiveness. These compositions may alsocontain other pesticides, stabilizers, conditioners, fillers and thelike.

The compounds of the present invention also possess insecticidalactivity. Representative compounds were tested as follows to illustratethe insecticidal properties. The test results are reported in Table III.

TEST PROCEDURES Two-spotted Mites (Tetranychus urticae)

An acetone solution of the candidate toxicant containing a small amountof nonionic emulsifier was diluted with water to 100 ppm. Pinto beanleaves which were infested with mites were dipped in the toxicantsolution. Mortality readings were taken after 24 hours.

Two-spotted Mite Eggs (Tetranychus urticae)

An Acetone solution of the candidate toxicant was prepared containing asmall amount of a nonionic surfactant. The acetone solution was dilutedwith water to give a 100 ppm solution. A primary leaf from Pinto beanswhich had been infested with mites 48 hours before and consequentlycontained mite eggs were immersed in the toxicant solution and thenallowed to dry at room temperature for seven days at 85°F. On the eighthday the egg mortality was rated on a scale of 0 to 11; 0 representing nokill, 11 representing 100% kill.

Aphids (Aphis gossypii Glover)

An acetone solution of the candidate toxicant containing a small amountof nonionic emulsifier was diluted with water to 30 ppm. Cucumber leavesinfested with the cotton aphids were dipped in the toxicant solution.Mortality readings were taken after 24 hours.

                                      TABLE III                                   __________________________________________________________________________                        % Control                                                                            Two-spotted                                                           Two-spotted                                                                          Mites                                                  Compound        Mites  Eggs   Aphids                                       __________________________________________________________________________    S,S-di-n-butyl-N,N-dimethyl                                                                      70     96     --                                           phosphoroamidodithionite                                                      S,S-n-butyl-N,N-di-n-propyl                                                                      --     100    --                                           phosphoroamidodithionite                                                      S,S-di-n-butyl     --     98     --                                           phosphoroamidodithionite                                                      S,S-di-n-butyl-N-methyl                                                                          99     --     99                                           phosphoroamidodithionite                                                      S,S-di-n-butyl-N-2-fluorophenyl                                                                  --     96     --                                           phosphoroamidodithionite                                                      S,S-diisopropyl-N-methyl                                                                         98     --     --                                           phosphoroamidodithionite                                                      S,S-diisopropyl-N-ethyl                                                                          100    --     96                                           phosphoroamidodithionite                                                      S,S-diethyl-N-ethyl                                                                              85     --     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-diethyl                                                                      97*    --     100                                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-dimethyl                                                                     100    --     100                                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-methyl                                                                         100    90     100                                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-piperidyl                                                                      100    96     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N,N-di-n-propyl                                                                  99     99     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-benzyl                                                                         100    99     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-allyl                                                                          99     --     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-2-fluorophenyl                                                                 70     100    --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-ethyl                                                                          100    90     94                                           phosphoroamidodithionite                                                      S,S-di-n-butyl-N-acetyl                                                                          96     96     94                                           phosphoroamidodithionite                                                      S,S-di-n-butyl-N-propionyl                                                                       --     98     --                                           phosphoroamidodithionite                                                      S,S-di-n-propyl-N-acetyl                                                                         100    100    100                                          phosphoroamidodithionite                                                      S,S-di-n-propyl-N-acetyl-N-phenyl                                                                100    --     96                                           phosphoroamidodithionite                                                      __________________________________________________________________________     *40 ppm?                                                                 

In general, the preferred compounds for use as insecticides are thosewherein R₁ and R₂ are individually propyl or butyl, R₃ is hydrogen,methyl, ethyl or propyl and R₄ is hydrogen, methyl, ethyl, propyl orfluorophenyl; or benzyl or allyl when R₁ and R₂ are propyl.

In addition to the specific formulations and application techniquesdescribed above, one or more of the compound derivatives of theinvention may be applied in other liquid or solid formulations to theinsects, their environment, or hosts susceptible to insect attack. Forexample, they may be sprayed or otherwise applied directly to plants orsoil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxicamount of one or more carbamate derivatives and a biologically inertcarrier. Usually they will also contain a wetting agent. Solid carrierssuch as clay, talc, sawdust and the like may be used in suchformulations. Liquid diluents which may be used with these compoundsinclude water and aromatic solvents. In addition these formulations maycontain other compatible pesticides, plant growth regulators, fillers,stabilizers, attractants and the like.

The concentration of the active ingredient to be used with inertcarriers, either solid or liquid carriers, will be dependent upon manyfactors, such as the particular carbamate compound which is used, thecarrier in or upon which it is incorporated, the method and conditionsof application, the insect species to be controlled, etc., the properconsideration of these factors being within the skill of these versed inthe art. In general, the toxic ingredients of this invention will beeffective in concentrations from about 0.0001 percent by weight to ashigh as 90 percent by weight or higher. Economically, of course, it isdesirable to use lower concentrations of this active ingredient. Thus,it is usually desirable to use less than 20 percent by weight of theactive ingredient in a particular composition.

The terms "insecticide" and "insect" as used herein refer to their broadand commonly understood usage rather than to those creatures which inthe strict biological sense are classified as insects. Thus, the term"insect" is used not only to include small invertebrate animalsbelonging to the class Insecta but also to other related classes ofarthropods whose members are segmented invertebrates having more orfewer than six legs, such as spiders, mites, ticks, centipedes, wormsand the like.

Some of the compounds of the present invention are also useful in thecontrol of nematodes and algae, for example Euglena.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

I claim:
 1. A compound of the formula ##EQU4## where R₁ is alkyl of 1 to8 carbon atoms or alkenyl of 2 to 8 carbon atoms, R₂ is alkyl of 1 to 8carbon atoms or alkenyl of 2 to 8carbon atoms, and R₃ and R₄ are jointedto form an alkylene group of 2 to 5 carbon atoms.
 2. The compound ofclaim 1 wherein R₁ and R₂ are independently alkyl of 1 to 4 carbonatoms.
 3. The compound of claim 1 wherein R₁ and R₂ are independentlyalkyl of 3 to 4 carbon atoms.
 4. S,S-di-n-propyl-N-piperidylphosphoroamidothionite, according to claim
 1. 5.S,S-di-n-butyl-N-pyrrolidyl phosphoroamidodithionite, according toclaim
 1. 6. S,S-di-n-octyl-N-piperidyl phosphoroamidodithionite,according to claim
 1. 7. A compound of the formula ##EQU5## wherein R₁and R₂ are defined in claim 1 and R₃ and R₄ are joined with nitrogen toform a piperidyl, pyrrolidyl or morpholine group.